CN1436027A - Organic electroluminescent device used with Mg cathode and with adhesion-promoting layer - Google Patents
Organic electroluminescent device used with Mg cathode and with adhesion-promoting layer Download PDFInfo
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Abstract
An organic electroluminescent device is provided that includes an anode and a substantially pure Mg cathode, an electroluminescent medium disposed between the anode and the cathode, and an adhesion-promoting layer in contact with cathode and the electroluminescent medium. The adhesion-promoting layer comprises at least one metal or metal compound selected from group 1 through group 15 of the Periodic Table of Elements such that the metal has an atomic number of at least 19.
Description
Technical field
The present invention relates to organic electroluminescence device.More particularly, it relates to use novel cathode material.
Background technology
Organic electroluminescent (EL) device or Organic Light Emitting Diode (OLED) be the response add electromotive force and luminous electronic device.The structure of an OLED comprises an anode, an organic EL medium and a negative electrode successively.The organic EL medium that is disposed between this anode and this negative electrode comprises an organic hole migrating layer (HTL) and an organic electronic migrating layer (ETL) usually.Hole and electronics are compound and luminous at the ETL of HTL near interface.People such as Tang (Applied Physics Letters, 51,913 (1987), Journal of AppliedPhysics, 65,3610 (1989) and the common US-A-4 that transfers the possession of, 769,292) have confirmed to use the high efficiency OLED of a kind of layer of structure like this.Since then, many OLED that the substitutable layer structure is arranged are disclosed.
On the overall performance of OLED device, negative electrode plays a significant role.It injects electronics at run duration to ETL.Yet, in OLED, between metallic cathode and organic ETL, adhesion problem is often arranged.Owing to the bonding bad this rough interfaces that causes causes device performance bad, for example driving voltage is higher, luminous efficiency is lower and service life is shorter between negative electrode and the organic layer.
Metallic cathode of being mentioned and the adhesion problem between the organic layer be existing the discussion in Tang and VanSlyke (US-A-4,885,211).Have been found that at Mg during the thermal evaporation not to be adhered to well on organic surface that this causes the sheet resistance height, film morphology is coarse and the device performance of Mg cathode device is bad.Therefore, Tang and VanSlyke disclose magnesium alloy negative electrode, for example Mg: Ag (US-A-4,885,211) and Al: Mg (US-A-5,059,862), and these alloy cathodes have improved bonding to ETL, and are that coevaporation by Mg and Ag or Al forms.With such Mg alloy cathode, OLED can reach than with the device more performance of pure Mg as negative electrode.Yet the making of Mg alloy cathode needs two thermal evaporation sources, and these two thermal evaporation sources must accurately be controlled just can guarantee appropriate alloy ratio.This dual-source evaporation must be more complicated than the evaporation of single source.With regard to Al: with regard to the Mg negative electrode, the thermal evaporation that the Al of suitable evaporation rate is arranged is unapproachable.
Many patent disclosures have been arranged use alkali metal compound (US-A-5,739,635), alkaline earth metal compound (US-A-5,457,565) and other material (US-A-6,013,384) is as the electron injecting layer (EIL) that uses with the Al anode.Specifically, lithium compound is by a kind of useful EIL material of extensively openly using as the Al negative electrode.Yet pure in fact Mg has some kinds of desirable characteristics, comprise low work content (～3.7eV) and excellent thermal evaporation character.Pure in fact Mg is not proved as yet as the purposes of the negative electrode among the high efficiency OLED.
Summary of the invention
An object of the present invention is to provide the OLED that excellent bonds is arranged between a kind of substantially pure magnesium negative electrode and the organic layer.
Another object of the present invention provides a kind of OLED that a magnesium evaporation negative electrode is arranged.
Another purpose again of the present invention is to improve the efficient of OLED, driving voltage and operation stability.
These purposes realize that with a kind of organic electroluminescence device this device comprises:
A) anode and a negative electrode;
B) electroluminescent medium that is disposed between this anode and this negative electrode;
C) adhesion-promoting layer that contacts with this electroluminescent medium with this negative electrode;
D) this adhesion-promoting layer has the thickness of 0.01～3.0nm, and comprises at least a metal or the metallic compound that is selected from the periodic table of elements the 1st family～the 15th family, makes this metal that at least 19 atomic number be arranged; With
E) this negative electrode is pure in fact magnesium.
Advantage
An advantage of the invention is, can make a kind of pure Mg cathode in fact can be used for high efficiency OLED.Very be surprised to find that the adhesion-promoting layer in 0.01nm～3.0nm thickness range can significantly improve Mg bonding on organic EL medium.
Another advantage of the present invention is, by at ETL and this adhesion-promoting layer of configuration between the pure Mg cathode in fact, also can improve EL efficient, driving voltage and the operation stability of this OLED.
Fig. 1 shows the schematic sectional view of a kind of prior art OLED;
Fig. 2 is a kind of schematic sectional view that disposes the OLED of an adhesion-promoting layer according to the present invention, between ETL and negative electrode;
Fig. 3 shows a kind ofly an evaporation Mg negative electrode is arranged but do not have the electroluminescence image that OLED produced of adhesion-promoting layer;
Fig. 4 shows an a kind of evaporation Mg negative electrode and electroluminescence image that OLED produced according to adhesion-promoting layer of the present invention is arranged that has;
Fig. 5 shows a kind of evaporation Mg that has: the Ag negative electrode but do not have adhesion-promoting layer OLED produced with reference to the electroluminescence image;
Fig. 6 shows the electroluminescence feature of the device that uses adhesion-promoting layer; With
Fig. 7 has compared a kind of Mg of having: the prior art OLED of Ag negative electrode and a kind of operation stability that has according to the OLED of Cs adhesion-promoting layer of the present invention and Mg negative electrode.
It being understood that Fig. 1 and Fig. 2 do not have dimensioning because each the layer all too thin and And the difference in thickness of each element allows too greatly and not designated size.
In order to understand more fully urging between the electron transfer layer of being disposed at and the negative electrode arranged among the present invention The structure of the OLED of adhesion coating and performance are described a kind of adhesion-promoting layer that do not have with reference to Fig. 1 OLED. Although take Fig. 1 as example, technical OLED known, that the substitutable layer structure is arranged is arranged earlier A lot. The present invention is applicable to any organic EL medium/cathode interface of containing OLED.
A kind of typically have earlier technology OLED structure to be shown as OLED 100 in Fig. 1. OLED 100 comprises a base material 101, an anode layer 103, an optional hole injection layer (HIL) 105, hole moving layers 107,109, electricity of a luminescent layer (LEL) Sub-migrating layer 111 and a negative electrode layer 113. These layers are in following detailed description.
OLED 100 be by apply a kind of by the voltage between anode 103 and negative electrode 113/ The electromotive force that current source 160 takes place so that for negative electrode 113 anode 103 be in corrigendum Current potential moves. Electric conductor 150 makes anode 103 and negative electrode 113 and voltage/current source 160 Connect. By applying a kind of electromotive force, make hole (positive charge carrier) from anode 103 via HIL 105 inject HTL 107. Simultaneously, make electronics (negative charge carrier) inject ETL from negative electrode 113 111. Hole and electronics are compound in LEL 109. This kind hole-electron recombination causes LEL 109 Luminous.
See now Fig. 2, OLED 200 of the present invention has one to be positioned at ETL 111 and negative electrode 240 Between adhesion-promoting layer 230. Other side, OLED 200 is similar to technology OLED 100 is arranged earlier Mode construct and move. Negative electrode 240 comprises in fact pure Mg. In fact purely be Refer to that the purity of this Mg negative electrode is greater than 90 volume %Mg, better greater than 99 volume %Mg, ideal Ground is greater than 99.9 volume %Mg. When using in fact pure magnesium as negative electrode, of the present invention Advantage is the most obvious.
As what mentioned in the past, in OLED, between Mg negative electrode and organic layer, usually An adhesion problem is arranged. It is disclosed as the people such as Tang (US-A-4,885,211), Pure Mg why can't thermal evaporation to organic surface and the reason that forms good contact is that Mg is not adhered on this organic surface well. US-A-4, the Fig. 4 in 885,211 demonstrates Mg negative electrode and Mg: the relative rough surface form of Ag negative electrode. Organic surface is not gold Belonging to atom provides enough coring positions to form a metallic film that good adhesion is arranged. Cause This, believe Mg on the organic layer surface (for example, at three (oxine) aluminium (III) On the layer surface) the Mg atom at first forms crystalline substance at these more lip-deep nucleation positions between depositional stage Nuclear. Because the shortage at nucleation position on this surface, the deposition of Mg atom causes these crystalline substances subsequently Nucleus growth becomes separately independently crystallite, causes the inhomogeneous and random distribution of crystallite, final formation Inhomogeneous negative electrode.
Yet the number at nucleation position can be used some surface modifications intentionally on this organic surface Method increases. In the present invention, have at this before the substantially pure Mg negative electrode deposition Depositing skim (so-called thin, mean that layer thickness is less than 3nm) on the machine surface better has and is different from The metal of the crystalline texture of Mg or metallic compound. Between depositional stage, the gold of this metallic compound Belong to atom or molecule can with reactive organic molecule, form and make this Mg atomic energy between Mg layer depositional stage subsequently, be adhered to the lip-deep coring position of modification. Although metallic atom or compound With the reaction on organic surface to bonding be desirable, shape on this organic layer surface simply Become metal or the metallic compound of nucleus also can improve the subsequently viscosity of Mg between the Mg depositional stage. This metal or metallic compound thin layer are the layers 230 among Fig. 2. When layer 230 deposition and with After the deposition of Mg negative electrode layer 240 in, the Mg atom is this organic lip-deep nucleation position shape Become nucleus. Because can there be the various crystalline textures that are different from pure Mg at these nucleation positions, because of And the spatial symmetry of Mg crystalline texture has reduced on these positions, and therefore, the crystal of Mg is given birth to Long having slowed down makes this Mg layer have more continuity. And then, because rear at this in layer 230 deposition Enough nucleation positions are arranged on organic surface, thereby independently the Mg crystallite can be easier separately Link together, and can be in that early the stage forms continuous film. Therefore, reached ETL 111 with Mg negative electrode 240 between very good contacting.
What this adhesion-promoting layer was used should have than good material: the crystal structure that a) is different from Mg; B) When needs low work content during than the better electronic injection of Mg negative electrode (＜3.7eV); And c) to this Low diffusion rate in the organic film. Road as known, Mg has hexagonal crystallographic texture. For more Effectively reduce the spatial symmetry and the microcrystalline growth that slows down nucleation initial stage Mg of Mg, should The material that adhesion-promoting layer uses better but the crystal structure that is not limited to have other kind, for example cube Crystallographic system, centroid cubic crystal system, body-centered cubic system, rhombohedral system, cubic crystallographic system or quadrature Crystallographic system. Low diffusion rate is to be at least 19 metal or metallization by the atomic number of metal wherein Compound provides. More particularly, utilizable useful materials comprises from unit in layer 230 Plain periodic table the 1st family～the 15th family select so that the atomic number of this metal is at least 19 Metal or metallic compound. Such material comprises the big alkali metal of atomic molar ratio Na, atom The alkaline-earth metal that amount is bigger than Mg, alkali rare earth metal and transition metal. These metals also can Use as the metallic compound that is higher oxidation state. Useful especially is simple metal salt, gold Belong to oxide and metal halide. The example that consists of the anion of simple metal salt comprises nitric acid Root, nitrite anions, sulfate radical, inferior sulfate radical, sulphur root, silicate, carbonic acid root, borate, Cross chlorate anions, phosphate radical, orthophosphite, acetic acid root, reach other carboxylic acid root.
The particularly useful metal that uses in the layer 230 comprises: Sb, Ge, Sn, Pb, Ga, Zn, Ni, Pd, Pt, Rh, Ir, Fe, Mn, Nb, La, Ce, Sm, Eu, Tb, Dy, Yb, Ca, Sr, Ba, K, Rb or Cs and compound thereof comprise simple salt, oxide and halogen Compound. When this adhesion-promoting layer 230 of hope also has low work content character, alkali metal, alkaline-earth metal, With rare earth metal comprise K, Rb, Cs, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, Or Yb and compound as defined above thereof are useful especially. Be noted that we make The people surprisingly finds, comprise the common low work function metal of Li or Na and metallic compound for Use among the present invention is not effective. Why accident is because these materials are well-known for this Ground is that for example aluminium is effective to other negative electrode material. By inference, its relatively little size causes institute Undesirable diffusion in this organic layer, thus the surface does not have enough when Mg deposits The nucleation position can be for utilizing.
The thickness of this adhesion-promoting layer is very important. Found useful thickness range 0.01～Between the 3nm, better between 0.05～2nm. Surprisingly, a thickness is thinned to ratio Just be enough to film for the Mg negative electrode at the also little adhesion-promoting layer of single layer coating of ETL 111 deposition Formation provides desirable nucleation position. If will higher work content (＞3.7eV) material be used for should Adhesion-promoting layer then should provide electricity by low work content Mg negative electrode (or other low work function metal negative electrode) Sub-injectability. In this case, the part on this organic layer surface should be directly and this The contact of Mg layer. Therefore, higher work content adhesion-promoting layer should be thinned to is enough to not form at this organic layer A full coating.
Be used for this adhesion-promoting layer if will hang down work function materials, then the electronic injection ability may be decided by this Low work function metal itself, therefore, the thickness of this adhesion-promoting layer can quite be thicker than one or two individual layer. Yet, owing to low work function metal especially alkali metal is extremely active to moisture and oxygen, thereby The use of the thick-layer of these materials may be undesirable, because they are at sporadic water Or corrosion-vulnerable (oxidation) under the existence of oxygen. This causes forming an electric insulation layer and from the moon The utmost point injects the barrier of electronics to the EL medium. Thickness range between desirable 0.01～3nm is The electronic injection ability of guaranteeing the negative electrode that makes up with this adhesion-promoting layer is without prejudice. That is, its electronics Injectability should be not less than the electronic injection ability of Mg negative electrode.
The present invention can be used for most of OLED device configurations. These comprise that to comprise one single The very simple structure of anode and negative electrode for example comprises anode and negative electrode to more complicated device The quadrature array with the passive matrix display that forms pixel and each pixel independently such as Active matrix displays with a kind of thin film transistor (TFT) (TFT) control.
The configuration that can successfully implement organic layer of the present invention is a lot. As above-mentioned, Shown a kind of typical structure among Fig. 2. Be noted that this base material can alternatively be positioned at In abutting connection with the place of negative electrode, perhaps in fact this base material can consist of this anode. In addition, these have Total total thickness of machine layer is better less than 500nm.
Base material 101 both can be that light transmission also can be lighttight, because of luminous intention direction different.Light transmission character is desirable for watching EL to launch via this base material.Usually adopt transparent glass or plastics under these circumstances.For the application of watching the EL emission via top electrode, the transmission feature of end supporter is unessential, thereby can be light transmission, light absorption or the light reflection.The base material of Shi Yonging includes but not limited to glass, plastics, semi-conducting material, pottery and circuit board material in this case.Certainly, in these device configurations, be necessary to provide a kind of optical transparency top electrode.
Conductivity anode layer 103 normally forms on this base material, and should be transparent or transparent in fact to interesting emission when watching the EL emission via this anode.The transparent anode material commonly used that uses among the present invention is tin indium oxide (ITO) and tin oxide, but other metal oxide also can work, comprising but be not limited to zinc oxide (IZO), magnesium oxide indium and the nickel oxide tungsten of adulterated al or indium.Except that these oxides, metal nitride for example gallium nitride, metal selenide for example zinc selenide and metal sulfide for example zinc sulphide also can be used for layer 103.For the application of watching EL emission via top electrode, the transmission feature of layer 103 is unessential, can use any electric conducting material, transparent, opaque or reflexively all can.The conductor example of this application includes but not limited to gold, iridium, molybdenum, palladium and platinum.Typical anode material, no matter whether printing opacity, and 4.1eV or bigger work content are arranged.Desirable anode material normally deposits with for example evaporation of any suitable means, sputter, chemical vapour deposition or electrochemical means.Anode can be with well-known photoetch method patterning.
Though be not always necessary, often usefully between anode 103 and hole moving layer 107, provide a hole injection layer 105.This hole-injecting material can be used for improving film forming character and the convenient hole injection in hole moving layer of organic layer subsequently.The suitable material of using in this hole moving layer includes but not limited to US-A-4, the porphyrin compound described in 720,432, and US-A-6, the plasma-deposited fluorocarbon polymer described in 208,075.It is reported that the instead of holes injection material that can be used in the organic EL device sees EP 0 891 121A1 and EP 1 029 909 A1 for details.
The hole moving layer 107 of this organic EL device contains for example aromatic nitrile base of at least a hole migration compound, wherein the latter is interpreted as such compound, it comprises at least one trivalent nitrogen atom, this nitrogen-atoms only with carbon atom bonding, be a member of aromatic ring one of at least in the middle of the carbon atom.In one form, aromatic uncle amine can be arylamine such as monoarylamine, diaryl amine, triarylamine or polymeric arylamine.Example monomer triarylamine is in people's such as Klupfel 3,180,730 illustrated mistakes.One or more vinyl groups and/or comprise that at least one triarylamine that contains active hydrogen group is disclosed in people's such as Brantley US-A-3 in other suitable replacements are in 567,450 and US-A-3,658,520.
The comparatively preferred aromatic uncle amine of one class is that those comprise at least two aromatic uncle amines parts, as US-A-4, and 720,432 and US-A-5, described in 061,569.This compounds comprises those of structural formula (A) representative.
Q wherein
1And Q
2Be independently selected from the aromatic uncle amine part, G connects the alkylidene group of base as arlydene, cycloalkylidene or carbon-carbon bond.In one embodiment, Q
1With Q
2One of at least comprise many ring fused rings structures, for example, naphthylene.When G was aromatic yl group, it was phenylene, biphenylene or naphthylene part easily.
One class is useful satisfy structural formula (A) and comprise two triarylamines triarylamine partly represented by structural formula (B):
R wherein
1And R
2Represent hydrogen atom, aromatic yl group or alkyl group independently of one another, perhaps R
1With R
2Representative constitutes the atom of a group of naphthene base together; And
R
3And R
4Represent aromatic yl group independently of one another, the latter can replace the amino group that diaryl replaces again, and (C) is indicated as structural formula:
R wherein
5And R
6Be independently selected from aromatic yl group.In one embodiment, R
5With R
6One of at least comprise many ring fused rings structures, for example, naphthalene.
Another kind of aromatic uncle amine is four aryl diamines.Four satisfying aryl diamines comprise two ammonia diaryl base groups, as by as indicated in the structural formula (C), connect by arylene group between the two.Four useful aryl diamines comprise those that represented by structural formula (D).
Wherein each Are is independently selected from arylene group such as phenylene or anthrylene part,
N is 1～4 integer, and
Ar, R
7, R
8And R
9Be independently selected from aromatic yl group.
In typical embodiment, Ar, R
7, R
8And R
9In have at least one to be many ring fused rings structures, for example, naphthalene.
Each can replace the alkyl of various said structure formula (A), (B), (C), (D), alkylidene, aryl and arlydene part again.Typical substituting group comprises alkyl group, alkoxy base, aromatic yl group, aryloxy group and halogen such as fluorine, chlorine and bromine.Various alkyl and alkylene moiety usually comprise about 1～6 carbon atom.Cycloalkyl moiety can comprise 3～about 10 carbon atoms but typically comprise 5,6 or 7 ring carbon atoms---for example, and the ring structure of cyclopenta, cyclohexyl and suberyl.Aryl and arlydene part be phenyl and phenylen moiety normally.
Hole moving layer can be made of single aromatic uncle amine compound or its mixture.Specifically, can adopt triarylamine, as satisfy the triarylamine of structural formula (B), with four aryl diamines, (D) is represented as structural formula, the combination of the two.When triarylamine and four aryl diamines are used in combination, the latter is sandwiched in triarylamine as a layer and electronics injects and migrating layer between.The example of useful aromatic uncle amine is a following compounds:
1,1-two (4-two-p-methylphenyl aminophenyl) cyclohexane
1,1-two (4-two-p-methylphenyl aminophenyl)-4-cyclohexylbenzene
4,4 '-two (diphenyl amino) quaterphenyl
Two (4-dimethylamino-2-aminomethyl phenyl)-phenylmethanes
N, N, N-three (p-methylphenyl) amine
4-(two-p-methylphenyl amino)-4 '-(4 (two-p-methylphenyl amino)-styryl) Stilbene
N, N, N ', N '-four-p-methylphenyl-4,4 '-benzidine
N, N, N ', N '-tetraphenyl-4,4 '-benzidine
N, N, N ', N '-four-1-naphthyl-4,4 '-benzidine
N, N, N ', N '-four-2-naphthyl-4,4 '-benzidine
The N-phenyl carbazole
4,4 '-two (N-(1-naphthyl)-N-phenyl amino) biphenyl
4,4 " two (N-(1-naphthyl)-N-(2-naphthyl) aminobphenyl
4,4 " two (N-(1-naphthyl)-N-phenyl amino) para-terpheny
4,4 '-two (N-(2-naphthyl)-N-phenyl amino) biphenyl
4,4 '-two (N-(3-acenaphthenyl)-N-phenyl amino) biphenyl
1,5-two (N-(1-naphthyl)-N-phenyl amino) naphthalene
4,4 '-two (N-(9-anthryl)-N-phenyl amino) biphenyl
4,4 " two (N-(1-anthryl)-N-phenyl amino)-para-terpheny
4,4 '-two (N-(2-phenanthryl)-N-phenyl amino) biphenyl
4,4 '-two (N-(8-fluoranthene base)-N-phenyl amino) biphenyl
4,4 '-two (N-(2-pyrenyl)-N-phenyl amino) biphenyl
4,4 '-two (N-(2-aphthacene base)-N-phenyl amino) biphenyl
4,4 '-two (N-(2-perylene base)-N-phenyl amino) biphenyl
4,4 '-two (N-(the cool base of 1-)-N-phenyl amino) biphenyl
2,6-two (di-p-tolyl amino) naphthalene
2,6-two (two-(1-naphthyl) amino) naphthalene
2,6-two (N-(1-naphthyl)-N-(2-naphthyl) amino) naphthalene
N, N, N ', N '-four (2-naphthyl)-4,4 " diaminourea-para-terpheny
4,4 '-two { N-phenyl-N-(4-(1-naphthyl)-phenyl) amino } biphenyl
4,4 '-two (N-phenyl-N-(2-pyrenyl) amino) biphenyl
2,6-two (N, N-two (2-naphthyl) amine) fluorenes
1,5-two (N-(1-naphthyl)-N-phenyl amino) naphthalene
Another kind of useful hole transporting material comprises polynuclear aromatic compound, as is described among the EP 1,009 041.In addition, the hole transporting material of polymerization also can also can use, and for example, poly-(N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline and copolymer be as poly-(3,4-ethylidene dioxy base thiophene)/poly-(4-styrene sulfonic acid), also claims PEDOT/PSS.
As describing in greater detail at US-A-4, like that, the luminescent layer of organic EL (LEL) 109 comprises luminous or fluorescent material, wherein owing to electron-hole pair produces electroluminescence in this region composite in 769,292 and US-A-5,935,721.Luminescent layer can be made up of homogenous material, forms jointly with one or more guest compounds but more commonly mixed by material of main part, and the wherein luminous dopant that mainly comes from can be any color also.Material of main part in the luminescent layer can be a kind of electron transfer material, as following defined, and a kind of hole transporting material, as top defined, or the material of another kind of support hole-electron recombination or the combination of material.Dopant is selected from the dyestuff of height fluorescence usually, but phosphorescent compound, for example, the transition metal complex of describing among WO 98/55561, WO 00/18851, WO 00/57676 and the WO 00/70655 also is useful.Dopant is applied in the material of main part with the quantity of 0.01～10wt% usually.
Select the comparison that important relationship be band gap gesture of dyestuff as dopant, the band gap gesture is defined as energy difference between the highest occupied molecular orbital of molecule and the lowest unoccupied molecular orbital.For realizing energy transfer efficiently from the main body to the dopant molecule, a necessary condition is the band gap of the band gap of this dopant less than material of main part.
Known useful host molecule and light emitting molecule include but not limited in the following patent application disclosed those: US-A-4,768,292; US-A-5,141,671; US-A-5,150,006; US-A-5,151,629; US-A-5,405,709; US-A-5,484,922; US-A-5,593,788; US-A-5,645,948; US-A-5,683,823; US-A-5,755,999; US-A-5,928,802; US-A-5,935,720; SU-A-5,935,721 and US-A-6,020,078.
The metal complex of oxine and like derivatives thereof (general formula E) constitute a class can support electroluminescent useful host compound, and is particularly suitable for sending the light of wavelength greater than 500nm, for example, and green, yellow, orange and ruddiness.
Wherein
M represents metal;
N is 1～4 integer; And
The each atom of representative formation independently that occurs of Z with nuclear of at least two fused aromatic rings.
By top described can clearly be seen that, metal can be monovalence, divalence, trivalent or tetravalence.This metal can be for example alkali metal such as lithium, sodium or potassium; Alkaline-earth metal such as magnesium or calcium; Perhaps earth metal is as aluminium or gallium; Or a kind of transition metal for example zinc or zirconium.Generally speaking, known any monovalence, divalence, trivalent or the tetravalent metal that can be used as chelated mineral all can use.
Z constitutes the heterocyclic nucleus that comprise at least two fused aromatic rings, and wherein at least one is pyrroles or azine ring.When needing, also other ring can be arranged, comprise aliphatic series and aromatic ring, can condense with the ring of these two requirements.But do not improve function for avoiding increasing molecular volume, the number of ring generally remains on and is equal to or less than 18.
The example of the class oxine compound of useful chelating is as follows:
CO-1: three oxine aluminium (another name, three (oxine closes) aluminium (III) or Alq)
CO-2: two oxine magnesium (another name, two (oxine closes) magnesium (II))
CO-3: two (benzo the f}-8-oxyquinoline closes) zinc (II)
CO-4: two (2-methyl-oxine closes) aluminium (III)-mu-oxo-two (2-methyl-oxine closes) aluminium (III)
CO-5: three oxine indiums (another name, three (oxine closes) indium)
CO-6: three (5-methyl oxine) aluminium (another name, three (5-methyl-oxine closes) aluminium (III))
CO-7: oxine lithium (another name, (oxine closes) lithium (I))
CO-8: oxine gallium (another name, three (oxine closes) gallium (III))
CO-9: oxine zirconium (another name, four (oxine closes) zirconium (IV))
9,10-two (2-naphthyl) anthracene derivant (general formula F) constitutes a class can support electroluminescent useful main body, and is particularly suitable for sending the light of wavelength greater than 400nm, for example, and blue, green, yellow, orange or ruddiness.
Wherein: R
1, R
2, R
3, R
4, R
5And R
6The one or more substituting groups of representative on each ring, wherein each substituting group is selected from following each group individually:
Group 1: hydrogen, or the alkyl of 1～24 carbon atom;
The aryl of group 2:5～20 carbon atom or the aryl of replacement;
Group 3: constitute needed 4～24 carbon atoms of fused aromatic rings such as an anthryl, pyrenyl Huo perylene base;
Group 4: constitute the heteroaryl that condenses 5～24 required carbon atoms of assorted aromatic rings of furyl, thienyl, pyridine radicals, quinolyl or other heterocycles system or the heteroaryl of replacement;
Alkoxy amino, alkyl amino or the arylamino of group 5:1～24 carbon atom; And
Group 6: fluorine, chlorine, bromine or cyano group.
Illustrative example comprises 9,10-two (2-naphthyl) anthracene and the 2-tert-butyl group-9,10-two (2-naphthyl) anthracene.Other anthracene derivant comprises 9, and the derivative of 10-two (4-(2, the 2-diphenylacetylene) phenyl) anthracene also can be used as the main body among the LEL.
Indole derivatives (general formula G) constitutes another kind ofly can support electroluminescent useful main body, and is particularly suitable for sending the light of wavelength greater than 400nm, for example, and blue, green, yellow, orange or ruddiness.
Wherein:
N is 3～8 integer;
Z is O, NR or S; And
R ' represents hydrogen separately; The alkyl of 1～24 carbon atom, for example, propyl group, the tert-butyl group, heptyl etc.; The aryl that the aryl of 5～20 carbon atoms or hetero-atom replace, for example, phenyl and naphthyl, furyl, thienyl, pyridine radicals, quinolyl and other heterocycles system; Perhaps halogen such as chlorine, fluorine; Perhaps for constituting the needed atom of fused aromatic rings;
The linkage unit that L is made up of the aryl of the alkyl of alkyl, aryl, replacement or replacement links together these a plurality of indoles with conjugation or non-conjugated mode.
The example of useful indoles is 2,2 ', 2 " (1,3, the 5-phenylene)-three (1-phenyl-1H-benzimidazole).
Desirable fluorescent dopants comprises the derivative of following compound: anthracene, aphthacene, xanthene, perylene, rubrene, cumarin, rhodamine, quinacridone, dicyano methylene pyrylium compound, thiapyran compound, polymethine compound, pyrilium and thiapyrilium compound and carbonyl styrene based compound.The example of useful dopant includes but not limited to following compounds:
The better film that the electron transfer layer 111 of organic EL device of the present invention forms usefulness the forms material class oxine compound of metal that has been chelating comprises the chelate of oxine (being also referred to as 8-quinolinol or oxine usually) itself.Such compound helps to inject and the migration electronics, and all demonstrates high-caliber performance, makes form of film easily.The class oxine examples for compounds of expectation is the above, can satisfies those of structural formula (E).
Other electron transfer material comprises US-A-4, disclosed various butadiene derivatives in 356,429, and US-A-4, the various heterocycle fluorescent whitening agents described in 539,507.The indoles that can satisfy structural formula (G) also is useful electron transfer material.
In some cases, layer 109 and 111 can randomly be merged into a simple layer, and performance had not only been supported luminous but also supported the function of electron transfer.In addition, polymeric material can constitute the main body among the LEL or serve as ETL or both have both at the same time.Such polymer comprises poly-to benzene divinyl (PPV), PPV derivative, poly-fluorenes and poly-fluorene derivative.
Negative electrode of the present invention encyclopaedizes.When via anode light, cathode layer 240 can have any useful thickness.When watching via negative electrode when luminous, this negative electrode must be transparent or be close to transparent.For such application, the Mg cathode layer must be that approach, better thick less than 25nm.Under these circumstances, can randomly on this thin Mg negative electrode, provide an optically transparent secondary cathode for example ITO to reduce total film resistor.When needs, can include but not limited to through mask deposition, US-A-5 by a lot of well-known methods, 276,380 and EP0732868 described in integral projection shelter, laser ablation and selective chemical steam deposition.
Above-mentioned organic material suitably deposits via distillation, but can deposit to improve film forming with optional binder from a kind of solvent.If this material is a kind of polymer, then solvent deposition is usually preferably.The material of the deposition that distils can from one usually by such as US-A-6, " cloth is being pressed close to the position distillation of this base material then to a kind of donor sheet material in the distillation that the tantalum material described in 237,529 is formed.The material blends layer can utilize the boat that independently distils separately, also can be with each material premix and from a single distillation boat or the coating of donor sheet material.Patterned deposition can be used projection mask, integral projection mask (SU-A-5,294,870), realize from space definition thermal dye transfer of donor sheet material (US-A-5,851,709 and US-A-6,066,357) and ink ejecting method (US-A-6,066,357).
Most of OLED devices are responsive to moisture and/or oxygen, therefore, they for example aluminium oxide, bauxite, calcium sulfate, clay, silica gel, zeolite, alkali metal oxide, alkaline earth oxide, sulfate or metal halide and perchlorate are sealed in a kind of inert atmosphere for example in nitrogen or the argon gas together with a kind of drier usually.Encapsulation and dry method include but not limited to US-A-6, those described in 226,890.
The patent of mentioning in this specification and the full content of other publication are classified this paper list of references as.
Embodiment
Following examples provide for further understanding of the present invention.For for simplicity, material and will represent with the following abbreviation that provides with the layer of its formation.
ITO: indium-tin-oxide is used for forming transparent anode 103 on glass baseplate
CFx: the fluorocarbon layer of polymerization is used for forming hole injection layer 121,221 at electroluminescent medium
NPB:4,4 '-two (1-naphthyl-N-phenyl amino) biphenyl is used for forming hole moving layer 107 at electroluminescent medium
Alq: three (oxine) aluminium (III), be used for electroluminescent medium form luminescent layer 109 and electron transfer layer 111 both
Mg: Ag=magnesium: silver (10: 1 volume ratios) is used to form negative electrode 113
Mg: pure in fact magnesium is used to form negative electrode 113 or 240.
The EL feature of the device of all making is all used a constant-current supply and a photometer assessment.Luminous efficiency and driving voltage are with 20mA/cm
2Current density measure.The electroluminescence image of some devices is taken with the CCD camera.Some devices suffer from room temperature.At 20mA/cm
2The stability test of following operation.
Embodiment 1 (comparative example): no adhesion-promoting layer/usual Mg: Ag alloy
A kind of Mg of having: being prepared as follows of the reference OLED (see figure 1) of Ag alloy cathode: a kind of glass baseplate that has been coated with a transparent ITO conductive layer with a kind of commercial cleaning glass instrument clean, drying.The oxidizability plasma treatment is used on the ITO surface subsequently, should surface conditioning becoming anode.By in RF plasma treatment process chamber, making CHF
3Decomposing gas, the thick CFx of deposition one deck 1nm on the ITO surface of cleaning.Then, this base material is transferred to carried out another floor deposition in another chamber.By in usual vacuum deposition chamber about 10
-6From a heating boat distillation, deposit following each layer in the following order under the vacuum of Torr:
(1) hole moving layer, 75nm is thick, is made up of NPB;
(2) luminescent layer and electron injecting layer (the two-layer one deck that is merged into), 60nm is thick, is made up of Alq;
(3) negative electrode, approximately 200nm is thick, and by Mg: Ag forms.
After these layer depositions, the device of made takes out from the settling chamber, transfers to the drying box from surrounding environment to encapsulate.This device architecture is designated as ITO/CFx/NPB/Alq/Mg: Ag.
This device typically has the driving voltage of 6.0V to pass through 20mA/cm
2EL efficient with 3.2cd/A.In Fig. 6 of driving voltage that has shown the OLED that makes up according to the present invention and normalized luminance value, this normalization luminosity with reference to OLED is 1.0.The electroluminescence image of this device is shown among Fig. 5.
In following examples, this adhesion-promoting layer and negative electrode separate with oblique line on form: adhesion-promoting layer/negative electrode.
Embodiment 2 (comparative example): no adhesion-promoting layer/Mg negative electrode
Prepared and comparative example 1 similar OLED, different is that this negative electrode is the Mg of purity＞99.9%.Contact non-constant between ETL and the Mg negative electrode.The electroluminescence image of this device is shown among Fig. 3.Voltage is too high and the electroluminescence degree is too low, can't mark in Fig. 6.
Embodiment 3 (the present invention): Cs/Mg negative electrode
Prepared and comparative example 2 similar OLED, different is before the Mg cathodic deposition, to have deposited an adhesion-promoting layer on the electron transfer layer top.Embodiment 3 has utilized the thick Cs metal of 0.1nm as adhesion-promoting layer.This device architecture is expressed as ITO/CFx/NPB/Alq/Cs/Mg.This device has than this comparison with reference to device (embodiment 1) high 10% luminous efficiency and the driving voltage of low 1.2V.These values are shown among Fig. 6, and the electroluminescence image of this device is shown among Fig. 4.
By the electroluminescence image of each device in comparison diagram 3,4 and 5, can learn the advantage of this adhesion-promoting layer.Fig. 3 shows a kind of electroluminescence image that evaporates Mg negative electrode (220nm is thick) but do not have the OLED of adhesion-promoting layer that has; Fig. 4 shows a kind of electroluminescence image that the OLED of an evaporation Mg negative electrode (also being 220nm) and an adhesion-promoting layer (0.1nm Cs layer) is arranged; Show a kind of thermal evaporation Mg that has with Fig. 5: the electroluminescence image of the OLED of Ag alloy cathode (220nm).These three kinds of devices had identical EL medium and ito anode originally.Be clear that from Fig. 3 the OLED that makes up without adhesion-promoting layer produces a lot of blackspots (non-light-emitting area) when activating this device.These blackspots are that electronics injects bad causing as the result of loose contact between Mg negative electrode and organic layer and in regional area.Equally distributed blackspot shows, during the initial stage nucleation stage of Mg deposition, because nucleation position shortage on this organic surface, the Mg atom has formed separately independently crystallite, and these separately independently crystallite before it is connected to form a kind of Mg film, stay many noncontact microcells.As shown in Figure 4, because contacting of improving between the Mg that provides of this adhesion-promoting layer and this organic layer, in the OLED that constructs with a thick Cs layer of the 0.1nm that deposits on this organic layer before the Mg deposition, blackspot density significantly reduces.Comparison diagram 4 and Fig. 5 as can be seen, have the blackspot density of the OLED of Cs/Mg negative electrode to be similar to or less than Mg is arranged: the blackspot density of the OLED of Ag alloy cathode.Alloy composite is Mg for example: the use of Ag can produce this organic layer as everyone knows and contact with excellence between this negative electrode.Be clear that,, need an adhesion-promoting layer that good contact the between metallic cathode and this organic layer is provided for the pure in fact Mg that will be used as negative electrode.
Except that certain luminous efficiency and driving voltage advantage, this adhesion-promoting layer has than Mg is arranged: the better operation stability of the device of Ag negative electrode.Fig. 7 has compared between embodiment 3 and the embodiment 1 at 20mA/cm
2Following operation stability in room temperature.Mg is arranged: the luminosity of the OLED of Ag negative electrode reduces by 10% when operation in 100 hours, but has the luminosity of the OLED of Cs/Mg negative electrode only to reduce about 5% when operation in 700 hours.
Embodiment 4 (comparative example): Li/Mg negative electrode
Embodiment 5 (the present invention): CsNO
3/ Mg negative electrode
Embodiment 6 (comparative example): LiF/Mg negative electrode
Embodiment 7 (the present invention): alkaline-earth metal/Mg negative electrode
Embodiment 7 is similar to embodiment 3, and different is that it utilizes the thick Ba metal of 0.5nm as adhesion-promoting layer.This device has than the luminous efficiency of reference device high about 3% and the driving voltage of low 1.0V.Its numerical value is shown among Fig. 6.
Embodiment 8～9 (the present invention): rare earth metal/Mg negative electrode
Embodiment 8 is similar to embodiment 3, and different is that it utilizes the thick Yb metal of 3.0nm as adhesion-promoting layer.This device has and is similar to this with reference to the luminous efficiency of device with than this driving voltage with reference to the low about 0.4V of device.Its numerical value is shown among Fig. 6.Embodiment 9 is similar to embodiment 3, and different is that it utilizes the thick Sm metal of 0.2nm as adhesion-promoting layer.This device have than this with reference to the luminous efficiency of device high about 11% and with this with reference to the similar driving voltage of device.Its numerical value is shown among Fig. 6.
Embodiment 10 (the present invention): rare earth compound/Mg negative electrode
Embodiment 10 is similar to embodiment 3, and different is that it utilizes the thick LaF of 0.5nm
3As adhesion-promoting layer.This device has than this with reference to the luminous efficiency of device high about 13% and the driving voltage of low about 0.4V.Its numerical value is shown among Fig. 6.
Embodiment 11 (the present invention): high work function materials/Mg negative electrode
Embodiment 11 is similar to embodiment 3, different is, its utilizes the thick Ge of 0.2nm that is formed by electron beam evaporation as adhesion-promoting layer, and this device has with this and hangs down the driving voltage of about 0.4V with reference to the similar luminous efficiency of device with than this with reference to device, and its numerical value is shown among Fig. 6.
Embodiment 12 (the present invention): transition metal/Mg negative electrode
Embodiment 12 is similar to embodiment 3, and different is, its utilizes the thick Pd of 0.2nm that is formed in beam evaporation by electricity as adhesion-promoting layer.This device have with this with reference to the similar luminous efficiency of device with than this driving voltage with reference to the low about 0.3V of device.Its numerical value is shown among Fig. 6.
Embodiment 13 (the present invention): transistion metal compound/Mg negative electrode
Embodiment 13 utilizes the thick ZnO of 0.2nm that is formed by electron beam evaporation as adhesion-promoting layer.This device have than this with reference to the luminous efficiency of device high about 7% and with this with reference to the similar driving voltage of device.Its numerical value is shown among Fig. 6.
Embodiment 14～16 (the present invention): alkali metal or alkali metal compound/Mg: Ag negative electrode
Prepared and comparative example 1 similar OLED device, different is, at Mg: before the Ag cathodic deposition, at adhesion-promoting layer of electron transfer layer top deposition.Embodiment 14 utilizes the thick Cs metal of 0.5nm as adhesion-promoting layer.This device has than this with reference to the luminous efficiency of device high 20% and the driving voltage of low 1.0V.Its numerical value is shown among Fig. 6.Embodiment 15 utilizes the thick cesium acetate (CsOOCCH of 0.5nm
3) as adhesion-promoting layer.This device has than this with reference to the luminous efficiency of device high about 7% and the driving voltage of low about 0.9V.Its numerical value is shown among Fig. 6.Embodiment 16 utilizes the thick cesium carbonate (Cs of 0.3nm
2CO
3) as adhesion-promoting layer.This device has than this with reference to the luminous efficiency of device high about 5% and the driving voltage of low about 0.6V.Its numerical value is shown among Fig. 6.
Embodiment 17 (comparative example): LiF/Mg: Ag negative electrode
Embodiment 17 is similar to embodiment 14, and different is that it utilizes the thick LiF replaced C of 0.5nm s as adhesion-promoting layer.This device have with this with reference to the similar luminous efficiency of device (embodiment 1), but driving voltage is disadvantageous, this is its high 0.4V.Its numerical value is shown among Fig. 6.
Embodiment 14～16 shows, uses the adhesion-promoting layer that the electroluminescence feature of the OLED device of 91% purity Mg negative electrode also can the application of the invention to be improved.Embodiment 17 is described as follows the fact: the commonly used electron injecting layer very effective for the Al negative electrode do not provide remarkable advantage for Mg base negative electrode.As mentioned above, the thin layer of believing these less metals or metallic compound is diffused in this organic layer too easily.Therefore, on this surface, do not have enough nuclearing centres to help form cathode thin film and improve bonding force.
Other characteristic of the present invention comprises as follows:
Organic electroluminescence device, wherein, this rare earth compound comprises the oxide of La, Ce, Sm, Eu, Tb, Dy or Yb.
Organic electroluminescence device, wherein, this negative electrode is the Mg of purity＞99%.
Organic electroluminescence device, wherein, this negative electrode is a purity greater than 99.9% Mg.
Organic electroluminescence device, wherein, this negative electrode is the alloy of Mg and Ag.
Organic electroluminescence device, wherein, between anode and negative electrode the configuration electroluminescent medium comprise one with this adhesion-promoting layer in abutting connection with, comprise Alq layer.
Organic electroluminescence device, wherein, this adhesion-promoting layer is between 0.05～2.0nm.
Claims (10)
1. an organic electroluminescence device comprises
A) anode and a negative electrode;
B) electroluminescent medium that is disposed between this anode and this negative electrode;
C) adhesion-promoting layer that contacts with this electroluminescent medium with this negative electrode;
D) this adhesion-promoting layer has the thickness of 0.01～3.0nm, and comprises at least a metal or the metallic compound that is selected from the periodic table of elements the 1st family～the 15th family, makes this metal that at least 19 atomic number be arranged; With
E) this negative electrode is pure in fact magnesium.
2. the organic electroluminescence device of claim 1, wherein, this adhesion-promoting layer comprises one or more alkali metal that are selected from K, Rb or Cs.
3. the organic electroluminescence device of claim 1, wherein, this adhesion-promoting layer comprises one or more alkaline-earth metal that are selected from Ca, Sr or Ba.
4. the organic electroluminescence device of claim 1, wherein, this adhesion-promoting layer comprises one or more alkali metal compounds, wherein this metal comprises K, Rb or Cs.
5. the organic electroluminescence device of claim 1, wherein, this adhesion-promoting layer comprises one or more alkaline earth metal compounds, wherein this metal comprises Ca, Sr or Ba.
6. the organic electroluminescence device of claim 1, wherein, this adhesion-promoting layer comprises one or more transition metal or transistion metal compound.
7. the organic electroluminescence device of claim 6, wherein, this transition metal comprises Sb, Ge, Sn, Pb, Ga, Zn, Ni, Pd, Pt, Rh, Ir, Fe, Mn or Nb.
8. the organic electroluminescence device of claim 6, wherein, this transistion metal compound comprises the oxide of Sb, Ge, Sn, Pb, Ga, Zn, Ni, Pd, Pt, Rh, Ir, Fe, Mn or Nb.
9. the organic electroluminescence device of claim 1, wherein, this adhesion-promoting layer comprises one or more rare earth metals or rare earth compound.
10. the organic electroluminescence device of claim 9, wherein, this rare earth metal comprises La, Ce, Sm, Eu, Tb, Dy or Yb.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/062,361 US6794061B2 (en) | 2002-01-31 | 2002-01-31 | Organic electroluminescent device having an adhesion-promoting layer for use with a magnesium cathode |
| US10/062361 | 2002-01-31 |
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| CN1436027A true CN1436027A (en) | 2003-08-13 |
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| CN03103153A Pending CN1436027A (en) | 2002-01-31 | 2003-01-31 | Organic electroluminescent device used with Mg cathode and with adhesion-promoting layer |
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| Country | Link |
|---|---|
| US (1) | US6794061B2 (en) |
| EP (1) | EP1335638B1 (en) |
| JP (1) | JP2003234196A (en) |
| KR (1) | KR20030066370A (en) |
| CN (1) | CN1436027A (en) |
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- 2003-01-20 DE DE2003600399 patent/DE60300399T2/en not_active Expired - Lifetime
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| CN108611591A (en) * | 2012-11-06 | 2018-10-02 | Oti领英有限公司 | Method for depositing conductive cladding on the surface |
| CN108611591B (en) * | 2012-11-06 | 2021-05-04 | Oti领英有限公司 | Method for depositing a conductive coating on a surface |
| US11145771B2 (en) | 2012-11-06 | 2021-10-12 | Oti Lumionics Inc. | Method for depositing a conductive coating on a surface |
| US11532763B2 (en) | 2012-11-06 | 2022-12-20 | Oti Lumionics Inc. | Method for depositing a conductive coating on a surface |
| US11764320B2 (en) | 2012-11-06 | 2023-09-19 | Oti Lumionics Inc. | Method for depositing a conductive coating on a surface |
| WO2018166026A1 (en) * | 2017-03-13 | 2018-09-20 | 武汉华星光电技术有限公司 | Oled display device and oled display apparatus |
| CN111146363A (en) * | 2020-01-02 | 2020-05-12 | 京东方科技集团股份有限公司 | Display device and preparation method thereof |
| CN111146363B (en) * | 2020-01-02 | 2022-11-01 | 京东方科技集团股份有限公司 | Display device and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003234196A (en) | 2003-08-22 |
| EP1335638B1 (en) | 2005-03-23 |
| DE60300399D1 (en) | 2005-04-28 |
| US6794061B2 (en) | 2004-09-21 |
| DE60300399T2 (en) | 2006-01-19 |
| US20030152801A1 (en) | 2003-08-14 |
| KR20030066370A (en) | 2003-08-09 |
| TW200303701A (en) | 2003-09-01 |
| EP1335638A1 (en) | 2003-08-13 |
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